EP1984418A2 - Polyurethan-elastomere mit allophanat-modifizierten isocyanaten - Google Patents

Polyurethan-elastomere mit allophanat-modifizierten isocyanaten

Info

Publication number
EP1984418A2
EP1984418A2 EP07763413A EP07763413A EP1984418A2 EP 1984418 A2 EP1984418 A2 EP 1984418A2 EP 07763413 A EP07763413 A EP 07763413A EP 07763413 A EP07763413 A EP 07763413A EP 1984418 A2 EP1984418 A2 EP 1984418A2
Authority
EP
European Patent Office
Prior art keywords
weight
molecular weight
polyisocyanate
isocyanate
elastomer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP07763413A
Other languages
English (en)
French (fr)
Inventor
Stephen J. Harasin
Richard R. Roesler
Rick V. Starcher
Carol L. Kinney
James Garrett
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Covestro LLC
Original Assignee
Bayer MaterialScience LLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bayer MaterialScience LLC filed Critical Bayer MaterialScience LLC
Publication of EP1984418A2 publication Critical patent/EP1984418A2/de
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/7806—Nitrogen containing -N-C=0 groups
    • C08G18/7818—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups
    • C08G18/7837—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups containing allophanate groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/161—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22
    • C08G18/163—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22 covered by C08G18/18 and C08G18/22
    • C08G18/165—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22 covered by C08G18/18 and C08G18/22 covered by C08G18/18 and C08G18/24
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/20—Heterocyclic amines; Salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/20—Heterocyclic amines; Salts thereof
    • C08G18/2045—Heterocyclic amines; Salts thereof containing condensed heterocyclic rings
    • C08G18/2063—Heterocyclic amines; Salts thereof containing condensed heterocyclic rings having two nitrogen atoms in the condensed ring system
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
    • C08G18/8006—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32
    • C08G18/8009—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203
    • C08G18/8022—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203 with polyols having at least three hydroxy groups
    • C08G18/8025—Masked aliphatic or cycloaliphatic polyisocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2120/00—Compositions for reaction injection moulding processes

Definitions

  • This invention relates to polyurethane elastomers which exhibit improved weather resistance and to a process for their production.
  • RIM reaction injection molding
  • the reaction mixture generally comprises an A-side based on polyisocyanates and a B-side based on organic compounds containing isocyanate-reactive hydrogen atoms, in addition to suitable chain extenders, catalysts, blowing agents, and other additives.
  • the polyisocyanates which are suitable for a commercial RIM process are the aromatic isocyanates such as, for example, diphenylmethane-4,4'-diisocyanate (i.e. MDI).
  • U.S. Patent 4,772,639 describes a process for the production of polyurethane moldings reacting organic polyisocyanates with organic compounds containing isocyanate-reactive hydrogen atoms in the presence of catalysts and auxiliary agents inside a closed mold.
  • the isocyanate component is based on (a1) mixtures of (i) 1-isocyanate-3,3,5- trimethyl-5-isocyanatomethyIcyclohexane (IPDI), and (ii) polyisocyanates containing isocyanurate groups prepared by the trimerization of a portion of the isocyanate groups of 1 ,6-diisocyanatohexane, or (a2) (i) IPDI and (iii) polyisocyanates containing isocyanurate groups prepared by the trimerization of a portion of the isocyanate groups of a mixture of 1 ,6- diisocyanatohexane and IPDI.
  • reaction mixtures are broadly disclosed as being suitable for RIM processing.
  • U.S. Patent 4,642,320 discloses a process for the preparation of a molded polymer comprising reacting inside a closed mold a reaction mixture comprising (a) an active hydrogen containing material comprising a primary or secondary amine terminated polyether having an average equivalent weight of at least 500, (b) at least one chain extender, and (c) a (cyclo)aliphatic polyisocyanate, polyisothiocyanate, or mixture thereof, wherein the NCX index is from about 0.6 to 1.5.
  • This process requires that component (a) have at least 25%, and preferably 50% of its active hydrogen atoms present in the form of amine hydrogens.
  • the specific chain extender comprises (1 ) at least one component selected from the group consisting of (a) a hydroxyl-containing material which is essentially free of aliphatic amine hydrogen atoms, and (b) aromatic amine-containing materials containing at least two aromatic amine hydrogen atoms and are essentially free of aliphatic amine hydrogen atoms; and (2) at least one aliphatic amine-containing material having at least one primary amine group and an average aliphatic amine hydrogen functionality of from about 2 to 16.
  • aromatic polyisocyanates and (cyclo)aliphatic polyisocyanates are disclosed as being suitable for this process. All of the working examples in this patent use aromatic isocyanates that may be polymeric in nature.
  • U.S. Patent 5,260,346 also discloses reaction systems for preparing elastomers via the RIM process. These systems require an allophanate modified polyisocyanate, a hydroxyl group containing polyol, and an aromatic polyamine in which at least one of the positions ortho to the amine group is substituted with a lower alkyl substituent.
  • U.S. Patent 5,502,147 describes (cyclo)aliphatic isocyanate based RIM systems. These (cyclo)aliphatic isocyanates have a viscosity of less than 20,000 mPa-s at 25°C, an NCO functionality of 2.3 to 4.0, and are modified by isocyanurate groups, biuret groups, urethane groups, allophanate groups, carbodiimide groups, oxadiazine-trione groups, uretdione groups, and blends thereof.
  • the B-side comprises a high molecular weight polyol and a low molecular weight chain extender in which the OH:NH ratio is from 1:1 to 25:1.
  • U. S. Patent 5,502,150 which is commonly assigned, discloses a RIM process which uses a hexamethylene diisocyanate prepolymer having a functionality of less than 2.3, an NCO content of 5 to 25%, and a monomer content of less than 2% by weight. This prepolymer is reacted with a high molecular weight isocyanate-reactive compound, a chain extender selected from diols and aminoalcohols, and a hydroxyl-based crosslinking compound containing no more than one aliphatic amine hydrogen atom.
  • a chain extender selected from diols and aminoalcohols
  • a hydroxyl-based crosslinking compound containing no more than one aliphatic amine hydrogen atom.
  • Light stable polyurethanes are also disclosed in U.S. Patents 5,656,677 and 6,242,555.
  • the polyurethanes of U.S. 5,656,677 comprise the reaction product of a (cyclo)aliphatic isocyanate with a compound containing isocyanate-reactive hydrogen atoms, in the presence of a chain extender and/or crosslinker, and a specific catalyst system.
  • the catalyst system comprises 1 ) at least one organic lead compound, 2) at least one organic bismuth compound, and/or 3) at least one organic tin compound.
  • 6,242,555 comprise the reaction product of A) isophorone diisocyanate trimer/monomer mixture having an NCO group content of 24.5 to 34%, with B) an isocyanate-reactive component, in the presence of C) at least one catalyst selected from organolead (II), organobismuth (III) and organotin (IV) compounds.
  • compositions comprise the reaction product of a (cyclo)aliphatic polyisocyanate having an NCO functionality of 2.0 to 4.0; with an isocyanate-reactive component comprising a relatively high molecular weight organic compound containing hydroxyl groups, amine groups or mixtures thereof; and a low molecular weight chain extender selected from diols, primary amines, secondary amines aminoalcohols and mixtures thereof; with the resultant composition having a crosslink density of at least 0.3 moles/kg.
  • an isocyanate component having an NCO group content of about 20 to about 45% by weight, a functionality of about 2.0 to about 2.7, and comprising a trimerized (cyclo)aliphatic polyisocyanate, with (2) a high molecular weight polyether polyol that is free of amine groups and a low molecular weight compound that is also free of amine groups, in the presence of (3) one
  • Application Serial Number 11/304,265, filed December 15, 2006, which is also commonly assigned, is directed to improved weather resistant polyurethane elastomers.
  • These elastomers comprise (1 ) an isocyanate component having an NCO group content of about 20 to about 45% by weight, a functionality of about 2.0 to about 2.7, and comprising a trimerized (cyclo)aliphatic polyisocyanate, with (2) a high molecular weight polyether polyol having low unsaturation, a low molecular weight compound that is free of amine groups, and, optionally, a low molecular weight compound that is amine-initiated, in the presence of (3) one or more catalysts.
  • Polyurethane elastomers are also described in U.S. Application Serial Number 11/300,957, file December 15, 2005, which is commonly assigned. These elastomers comprise (1) an allophanate modified isocyanate or prepolymer thereof, with (2) a high molecular weight polyether polyol having low unsaturation, a low molecular weight compound that is free of amine groups, and, optionally, a low molecular weight compound that is amine-initiated, in the presence of (3) one or more catalysts.
  • Advantages of the present invention include improved cure and simplified catalysis, without the need for a lead based catalyst.
  • the elastomers of the present invention exhibit improved flexural modulus. These elastomers are also believed to exhibit improved weather resistance.
  • This invention relates to polyurethane elastomers and to a process for their production.
  • polyurethane elastomers comprise the reaction product of: (A) a polyisocyanate component comprising (I) an allophanate-modified polyisocyanate having an NCO group content of about 15 to about 35% by weight, preferably of about 15 to about 25% by weight, and comprising the reaction product of:
  • a (cyclo)aliphatic polyisocyanate component having an NCO group content of about 25 to about 60%, preferably about 30 to about 50%, and
  • an organic alcohol selected from the group consisting of aliphatic alcohols containing from about 1 to about 36 carbon atoms, cycloaliphatic alcohols containing from about 5 to about 24 carbon atoms and aromatic alcohols containing from about 7 to about 12 carbon atoms in which the alcohol group is not directly attached to an aromatic carbon atom; with
  • an isocyanate-reactive component comprising: (1 ) from about 70 to about 90% by weight, based on 100% by weight of (B), of one or more polyether polyols having a functionality of from about 2 to about 8 (preferably 2 to 4), a molecular weight of about 1000 to about 8,000 (preferably 2000 to 6000) and is free of (primary, secondary and/or tertiary) amine groups; and
  • m represents an integer from 3 to 8, preferably from 3 to 4
  • nn represents an integer from 3 to 8, preferably from 3 to 5
  • additives including ultraviolet stabilizers, pigments etc.
  • the relative amounts of components (A) and (B) are such that the isocyanate index of the resultant elastomer ranges from about 100 to about 120, preferably 105 to 110.
  • the allophanate modified polyisocyanates may be further reacted with an isocyanate-reactive component having a functionality of about 2 to about 6 and a molecular weight of about 60 to about 4,000 to form a prepolymer.
  • the resultant prepolymers typically have an NCO group content of about 10 to about 30% by weight.
  • These prepolymers of allophanate modified (cyclo)aliphatic polyisocyanates may also be used as component (A) in accordance with the present invention.
  • Suitable polyoisocyanates for the present invention comprise (I) at least one allophanate modified (cyclo)aliphatic polyisocyanate. It is also possible that the polyisocyanates of the present invention comprise a prepolymer of these allophanate modified (cyclo)aliphatic polyisocyanates.
  • Suitable allophanate modified polyioscyanates suitable for the present invention typically have an NCO group content of about 15 to about 35% by weight, and preferably of about 15 to about 25% by weight.
  • These allophanate modified polyisocyanates comprise the reaction product of (1 ) a (cyclo)aliphatic polyisocyanate which has an NCO group content of about 25 to about 60% by weight, and (2) an organic alcohol selected from the group consisting of aliphatic alcohols, cycloaliphatic alcohols and aromatic alcohols.
  • Suitable (cyclo)aliphatic polyisocyanates to be used as (1) in preparing the allophanate modified polyisocyanates (A)(I) of the present invention include, for example, 1 ,4-tetramethylene diisocyanate, 1,6- hexamethylene diisocyanate, 2,2,4-trimethyM ,6-hexamethylene diisocyanate, 1 ,12-dodecamethylene diisocyanate, cyclohexane-1 ,3- and - 1 ,4-diisocyanate, i-isocyanato-2-isocyanatomethylcyclopentane, 1- isocyanato-3-isocyanatomethyl-3,5,5-trimethylcyclohexane (i.e.
  • IPDI isophorone diisocyanate or IPDI), bis-(4-isocyanatocyclohexyl)methane, 2,4'- dicyclohexylmethane diisocyanate, 1,3- and 1,4-bis- (isocyanatomethyl)cyclohexane, bis-(4-isocyanato-3-methylcyclo- hexyl)methane, , ⁇ , ⁇ '-tetramethyl-1,3- and/or -1 ,4-xylylene diisocyanate, 1 -isocyanato-1 -methyl-4(3)-isocyanatomethylcyclohexane, dicyclohexylmethane-4,4'-diisocyanate, 2,4- and/or ,6-hexahydrotoluylene diisocyanate, and mixtures thereof.
  • the isocyanate comprise 1 ,6-hexamethylene diisocyanate, dicyclohexylmethane-4,4'- diisocyanate, and 1-isocyanato-3-isocyanatomethyl-3,5,5- trimethylcyclohexane.
  • Suitable organic alcohols include aliphatic alcohols, cycloaliphatic alcohols and aromatic alcohols in which the alcohol group is not directly attached to an aromatic carbon atom.
  • the aliphatic alcohols suitable for use as component (2) in preparing the allophanate-modified include those which contain from about 1 to about 36 carbon atoms, and preferably from about 1 to about 8 carbon atoms.
  • Suitable cycloaliphatic alcohols include those which contain from about 5 to about 24 carbon atoms, and preferably from about 6 to about 10 carbon atoms.
  • Suitable aromatic alcohols include those which contain from about 7 to about 12 carbon atoms, and preferably from about 8 to about 10 carbon atoms. In the aromatic alcohols suitable for the invention, the alcohol group is not directly attached to an aromatic carbon atom.
  • suitable organic alcohols include, for example, aliphatic alcohols such as methanol, ethanol, propanol, isopropanol, n- butanol, isobutanol, n-pentanol, 1-methylbutyl alcohol, cetylalcohol, 2- methoxyethanol, 2-bromo-ethanol, etc.; cycloaliphatic alcohols such as cyclohexanol, cyclopentanol, cycloheptanol, hydroxymethyl cyclohexanol, etc.; and aromatic alcohols in which the alcohol group is not directly attached to an aromatic carbon atom such as, for example, benzyl alcohol, 2-phenoxy ethanol, cinnamyl alcohol, p-bromobenzyl alcohol, etc.
  • aliphatic alcohols such as methanol, ethanol, propanol, isopropanol, n- butanol, isobutanol, n-pentanol, 1-methyl
  • Allophanate modified polyisocyanates of hexamethylene diisocyanate (HDI) typically have an NCO content of 15 to 45%, and preferably 20 to 30% by weight.
  • Allophanate modified polyisocyanates of dicyclohexylmethane diisocyanate (rMDI) typically have an NCO content of 15 to 35% and preferably 20 to 30% by weight.
  • Allophanate modified polyisocyanates of isophorone diisocyanate (IPDI) typically have an NCO content of 15 to 35%, and preferably 20 to 30% by weight.
  • Allophanate modified polyisocyanates of the (cyclo)aliphatic polyisocyanates which are suitable for the present invention are prepared in the known manner.
  • the (cyclo)aliphatic polyisocyanate is reacted with a suitable organic alcohol, in the presence of an allophanate catalyst at temperatures of about 60 to about 120 0 C, to form the allophanate modified polyisocyanate.
  • Suitable allophanate catalysts include, for example, zinc acetylacetonate, zinc 2-ethylhexanoate, cobalt naphthenate, lead linoresinate, etc. Typically, these catalysts are neutralized or otherwise stopped from adversely affecting subsequent reaction by the addition of a catalyst stopper.
  • Suitable catalyst stoppers include acidic materials such as, for example, anhydrous hydrochloric acid, sulfuric acid, bis(2- ethylhexyl)hydrogen phosphate, benzoyl chloride, Lewis acids, etc.
  • the stopper is typically added in a ratio of about 2 equivalents of the acidic stopper to each mole of the allophanate catalyst.
  • prepolymers of these allophanate modified polyisocyanates described above are also suitable to be used as the polyisocyanate component.
  • These prepolymers typically have an NCO group content of about 10 to about 35%, preferably from about 12 to about 25% by weight.
  • the prepolymers typically have a functionality of at least about 2.
  • These prepolymers also typically have a functionality of no more than about 6.
  • Preparation of the prepolymer of the allophanate modified polyisocyanates of the present invention comprises reacting these allophanate modified (cyclo)aliphatic poiyisocyanates as described above with a suitable isocyanate-reactive compound, such as, for example, a polyether polyol, polyester polyol, or low molecujar weight polyol including diols and triols.
  • a suitable isocyanate-reactive compound such as, for example, a polyether polyol, polyester polyol, or low molecujar weight polyol including diols and triols.
  • the isocyanate- reactive compounds suitable for the present invention typically have a molecular weight of about 60 to about 4,000 and have a hydroxyl functionality of about 2 to about 6.
  • suitable isocyanate- reactive compounds for forming the prepolymers of the allophanate modified polyisocyanates typically have a molecular weight of at least about 60, preferably of at least about 75, more preferably at least about 100, and most preferably at least about 130.
  • These isocyanate-reactive compounds also typically have a molecular weight of less than or equal to about 4,000, preferably of less than or equal to about 1 ,000, more preferably less than or equal to about 400, and most preferably less than or equal to about 200.
  • the isocyanate-reactive compounds useful herein may have a molecular weight ranging between any combination of these upper and lower values, inclusive, e.g., from about 60 to about 4,000, preferably from about 75 to about 1 ,000, more preferably from about 100 to about 400, and most preferably from about 130 to about 200.
  • suitable isocyanate- reactive compounds for forming the prepolymers of the allophanate modified polyisocyanates typically have a hydroxyl functionality of at least about 2, and typically less than or equal to about 6, preferably of less than or equal to about 4, and more preferably less than or equal to about 3.
  • the isocyanate-reactive compounds useful herein may have a hydroxyl functionality ranging between any combination of these upper and lower values, inclusive, e.g., from about 2 to about 6, preferably from about 2 to about 4, and more preferably from about 2 to about 3.
  • Suitable isocyanate-reactive compounds include polyether polyols, polyester polyols, low molecular weight polyols including diols, triols, etc. Obviously, the above limits on molecular weight and functionality apply to each of these groups of compounds. All of these compounds are known in the field of polyurethane chemistry.
  • Suitable polyether polyols may be prepared by the reaction of suitable starting compounds which contain reactive hydrogen atoms with alkylene oxides such as, for example, ethylene oxide, propylene oxide, butylene oxide, styrene oxide, tetrahydrofuran, epichlorohydrin, and mixtures thereof.
  • alkylene oxides such as, for example, ethylene oxide, propylene oxide, butylene oxide, styrene oxide, tetrahydrofuran, epichlorohydrin, and mixtures thereof.
  • Suitable starting compounds containing reactive hydrogen atoms include compounds such as, for example, ethylene glycol, propylene glycol, butylene glycol, hexanediol, octanediol, neopentyl glycol, cyclohexanedimethanol, 2-methyl-1 ,3-propanediol, 2,2,4-trimethyl- 1 ,3-pentanediol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dlpropylene glycol, polypropylene glycol, dibutylene glycol, polybutylene glycol, glycerine, trimethylolpropane, pentaerythritol, water, methanol, ethanol, 1 ,2,6-hexane triol,1 ,2,4-butane triol, trimethylol ethane, mannitol, sorbitol, methyl glycoside, sucrose, phenol, re
  • Suitable polyester polyols include, for example, the reaction products of polyhydric, preferably d ⁇ hydric alcohols (optionally in the presence of trihydric alcohols), with polyvalent, preferably divalent, carboxylic acids.
  • polyhydric preferably d ⁇ hydric alcohols (optionally in the presence of trihydric alcohols)
  • polyvalent preferably divalent, carboxylic acids.
  • carboxylic acids instead of using the free carboxylic acids, it is also possible to use the corresponding polycarboxylic acid anhydrides or corresponding polycarboxylic acid esters of lower alcohols or mixtures thereof for producing the polyesters.
  • the polycarboxylic acids may be aliphatic, cycloaliphatic, aromatic, and/or heterocyclic and may be unsaturated or substituted, for example, by halogen atoms.
  • the polycarboxylic acids and polyols used to prepare the polyesters are known and described for example in U.S.
  • Patents 4,098,731 and 3,726,952 herein incorporated by reference in their entirety.
  • Suitable polythioethers, polyacetals, polycarbonates and other polyhydroxyl compounds are also disclosed in the above-identified U.S. Patents.
  • representatives of the many and varied compounds which may be used in accordance with the invention may be found, for example, in High Polymers, Volume XVI, "Polyurethanes, Chemistry and Technology," by Saunders-Frisch, lnterscience Publishers, New York,
  • Suitable low molecular weight polyols for preparing prepolymers include, for example, diol, triols, tetrols, and low molecular weight alkoxylation products of these. These include 2-methyl-1 ,3-propanediol, ethylene glycol, 1 ,2- and 1 ,3-propanediol, 1 ,3- and 1,4- and 2,3- butanediol, 1 ,6-hexanediol, 1 ,10-decanediol, diethylene glycol, Methylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, glycerol, trimethylolpropane, neopentyl glycol, cyclohexanedimethanol, 2,2,4-trimethylpentane-1,3- diol, pentaerythritol, etc. Alkoxylation products of these same compounds may also be used to prepare prepoly
  • a preferred group of polyisocyanates useful herein include the prepolymers of allophanate-modified (cyclo)aliphatic polyisocyanates. These polyisocyanates are prepared by first, forming the allophanate- modified (cyclo)aliphatic poiyisocyanate as described above, and then reacting the allophanate-modified poiyisocyanate with a suitable isocyanate-reactive compound to form the prepolymer. This reaction is well known in the field of polyurethane chemistry, and can be carried out by, for example, heating the reactants to a temperature of from about 40 to about 150 0 C, preferably from about 50 to about 100 0 C , to yield the desired prepolymer. Obviously, an excess quantity of allophanate- modified poiyisocyanate to isocyanate-reactive compound is used.
  • Preferred allophanate modified polyisocyanates in accordance with the present invention include those selected from the group consisting of hexamethylene diisocyanate, isophorone diisocyanate and dicyclohexylmethane diisocyanate.
  • the resultant prepolymers of allophanate modified hexamethylene diisocyanate have a NCO group content of about 12 to about 35, preferably about 15 to about 25, and a functionality of about 2 to about 6 and preferably about 2 to about 3.
  • the resultant prepolymers of allophanate modified isophorone diisocyanate have a NCO group content of about 10 to about 35, preferably about 15 to about 25, and a functionality of about 2 to about 6 and preferably about 2 to about 3.
  • the resultant prepolymers of allophanate modified dicyclohexylmethane diisocyanate have a NCO group content of about 10 to about 35, preferably about 15 to about 25, and a functionality of about 2 to about 6 and preferably about 2 to about 3.
  • residues of isocyanates which may inherently result in the production of some of the above described isocyanates are not suitable for the isocyanate component herein. Such residues are undesirable by-products of the process for the production of the isocyanate components.
  • Suitable compounds to be used as component (B)(1) in accordance with the present invention include, for example, polyether polyols.
  • the high molecular weight polyethers suitable for use in accordance with the invention are known and may be obtained, for example, by polymerizing tetrahydrofuran or epoxides such as, for example, ethylene oxide, propylene oxide, butylene oxide, styrene oxide or epichlorohydrin in the presence of suitable catalysts, such as, for example, BF 3 or KOH, or by chemically adding these epoxides, preferably ethylene oxide and propylene oxide, in admixture, alone or successively to suitable starter compounds which contain reactive hydrogen atoms.
  • epoxides such as, for example, ethylene oxide, propylene oxide, butylene oxide, styrene oxide or epichlorohydrin
  • suitable catalysts such as, for example, BF 3 or KOH
  • starter compounds include, but are not limited to, propylene glycol, glycerin, ethylene glycol, butylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, water, trimethylolpropane, tetraethylene glycol, pentaerythritol, bisphenol A, sucrose, sorbitol, etc.
  • polyether polyols contain relatively high amounts of unsaturation.
  • Preferred polyethers include, for example, those alkoxylation products (preferably of ethylene oxide and/or propylene oxide) based on di- ortri-functional starters such as, for example, water, ethylene glycol, propylene glycol, glycerin, trimethylolpropane, etc.
  • Suitable compounds to be used as (B)(1) in accordance with the present invention include those having a molecular weight of from about 1 ,000 to about 8,000, preferably 2,000 to about 6,000, and a hydroxyl functionality of about 2 to about 8, and preferably of about 2 to about 4.
  • compounds suitable for component (B)(1 ) herein are free of primary, secondary and/or tertiary amine groups.
  • Suitable compounds to be used as (B)(2) in accordance with the present invention include those having a molecular weight of from about 62 to about 400, a hydroxyl functionality of about 2 or 3 and which are free of primary, secondary and/or tertiary amine groups. These compounds preferably have a molecular weight of from about 62 to about 90.
  • (B)(2) herein include compounds such as 2-methyl-1 ,3-propanediol, ethylene glycol, 1 ,2- and 1 ,3-propanediol, 1 ,3- and 1 ,4- and 2,3- butanediol, 1 ,6-hexanediol, 1 ,10-decanediol, diethylene glycol, Methylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, cyclohexanedimethanol, and 2,2,4- trimethylpentane-1 ,3- diol, trimethylolpropane, pentaerythritol, glycerol.
  • Preferred diols include, for example, ethylene glycol, and trimethylol propane.
  • reaction of component (A) with component (B) is in the presence of (C) one or more catalysts corresponding to the formula:
  • n represents an integer from 3 to 8, preferably from 3 to 5.
  • Suitable catalysts which correspond to the above identified formula include 1 ,8-diaza-7-bicyclo[5.4.0]undec-7-ene (i.e. DBU), 1 ,5-diazabicyclo[4.4.0]dec-5-ene (i.e. DBD), 1 ,5-diazabicyclo- [4.3.0]non-5-ene (i.e. DBN), 1 ,8-diazabicyclo[7.5.0]tetra-dec-8-ene, 1 ,8- diazabicyclo[7.4.0]tridec-8-ene, 1 ,8-diazabicyclo[7.3.0]-dodec-8-ene, etc.
  • DBU 1 ,8-diaza-7-bicyclo[5.4.0]undec-7-ene
  • DBD 1 ,5-diazabicyclo[4.4.0]dec-5-ene
  • DBN 1 ,5-diazabicyclo- [4.3.
  • the amount of catalyst corresponding to the above structure present is such that there is at least about 0.1% to about 6.0% by weight, preferably from about 0.5% to about 2.5%, and more preferably from about 1% to about 1.5% by weight, based on 100% by weight of component (B).
  • Suitable catalysts include, for example, the known metal carboxylates, metal halides, ammonium carboxylates, tin-sulfur catalysts, and tertiary amine catalysts.
  • Suitable metals for these catalysts include, but are not limited to, tin, bismuth, lead, mercury, etc. Of these catalysts, it is preferred to use tin carboxylates and/or tertiary amines in combination with the above described "diazabicyclo" catalysts.
  • Suitable metal carboxylates include tin carboxylates such as, for example, dimethyltin dilaurate, dibutyltin dilaurate, dibutyltin di-2-ethyl- hexoate, dibutyltin maleate, and bismuth carboxylates, such as, for example, bismuth trineodecanoate.
  • metal halides include, for example, tin halides and particularly, tin chlorides such as, for example, dimethyltin dichloride and dibutyltin dichloride.
  • Suitable examples of ammonium carboxylates include, for example, trimethyl- hydroxyethylarnmoniurn-2-ethylhexanoate (i.e. Dabco TMR).
  • tin carboxylates such as, for example, dimethyltin dilaurate, and dibutyltin dilaurate are preferred metal carboxylate catalysts to be used in conjunction with the above described catalysts of the specified formula.
  • Other suitable catalysts include tin-sulfur catalysts such as, for example, dialkyltin dilaurylmercaptides such as, for example, dibutyltin dilaurylmercaptide and dimethyltin dilaurylmercaptide.
  • tertiary amine catalysts include compounds such as, for example, triethylamine, triethylenediamine, tributylamine, N-methyl- morpholine, N-ethylmorpholine, triethanolamine, triisopropanolamine, N- methyldiethanolamine, N-ethyldiethanolamine, and N,N-dimethylethanol- amine.
  • a catalyst which corresponds to the formula set forth above in combination comprising one or more tin carboxylate catalysts.
  • Preferred tin carboxylates comprise dimethyltin dilaurate and/or dibutyltin dilaurate.
  • the total amount of both catalysts should generally fall within the quantities previously disclosed.
  • the total amount of all catalysts present should be such that there is at least about 0.1% to about 6.0% by weight of all catalysts, preferably from about 0.5% to about 2.5%, more preferably from about 1% to about 1.5% by weight of all catalysts, based on 100% by weight of component (B).
  • the amine catalyst (of the above structure) is present in an amount of from 50 to 90% by weight, and the tin carboxylate catalyst is present in an amount of from 10 to 50% by weight, with the sum of the %'s by weight totaling 100% by weight of the catalyst component.
  • Suitable stabilizers for the present invention include light stabilizers which are considered to include any of the known compositions which are capable of preventing significant yellowing in the elastomers of the present invention. As used herein, light stabilizer may be understood to include hindered amine light stabilizers, ultraviolet (UV) absorbers, and/or antioxidants.
  • hindered amine light stabilizers include, but are not limited to, compounds such as, for example, those derived from 2,2,6,6-tetraalkylpiperidine moieties, other types of hindered amines such as those containing morpholinones, piperazinones, piperazindiones, oxazolidines, imidazolines, and the like.
  • hindered amine light stabilizers include compounds such as, but are not limited to, bis(2 ) 2 I 6,6-tetramethyl-4-piperidyl)sebacate, bis(1 ,2,2,6,6- pentamethyl-4-piperidyl)sebacate, 2-methyl-2-(2,2,6,6-tetramethyl-4- piperidyl)amino-N-(2,2,6,6-tetramethyl-4-piperidyl)propionamide, bis(1,2,2,6,6-pentamethyl-4-piperidyl)-2-(3,5-di-tert-butyl-4- hydroxybenzyl)-2-n-butylmalonate, tetrakis(2,2,6,6-tetramethyl-4- piperidyl)-1 ,2,3,4-butanetetracarboxylate, poly[ ⁇ 6-(1 ,1 ,3,3- tetramethylbutyl)imino-1,3,5-triazine-2,
  • the benzofranone stabilizers include compounds such as, for example, 5,7-di-tert-butyl-3-(3,4-dimethylphenyl)-3H-benzofuran-2-one and the like.
  • the semicarbazide stabilizer includes, for example, 1 ,6- hexamethylenebis(N,N-dimethylsemicarbazide), 4,4'-(methylenedi-p- phenylene)bis(N,N-diethylsemicarbazide), 4,4'-(methylenedi-p- phenylene)bis(N,N-diethylsemicarbazide), 4,4'-(methylenedi-p- phenylene)bis(N,N-diisopropylsemicarbazide), ⁇ , ⁇ -(p-xylylene)bis(N,N- dimethylsemicarbazide), 1 ⁇ -cyclohexylenebisCN.N-dimethylsemi- carbazide)
  • Suitable ultraviolet (UV) stabilizers for the present invention include compounds such as, for example, 2-(3-tert-butyl-2-hydroxy-5-methyl- phenyl)-5-chlorobenzotriazole, 2-(3,5-di-tert-butyl-2-hydroxyphenyl)benzo- triazole, 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-tert- octylphenyl)benzotriazole, 2-(3,5-di-tert-amyl-2-hydroxyphenyl)benzo- triazole, 2-[2-hydroxy-3,5-bis( ⁇ , ⁇ -dimethylbenzyl)phenyl]benzotriazole, 2- hydroxy-4-octoxybenzophen ⁇ ne, 2-hydroxy-4-methoxybenzophenone, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, n-hexadec
  • alkylated monophenols such as, for example, 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-dicyclopentyl-4-methylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6- tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, etc.
  • alkylated hydroquinones such as, for example, 2,6-di-tert-butyl-4- methoxyphenol, 2,5-di-tert-butyl-hydroquinone, 2,5-di-tert-amyl-hydro- quinone, 2,6-diphenyl-4-octadecyloxyphenol, etc.
  • hydroxylated thio- diphenyl ethers such as, for example, 2,2 l -thio-bis-(6
  • one or more pigments and/or dyes may also be present.
  • Suitable inorganic pigments include, for example, oxide pigments such as iron oxides, titanium dioxide, nickel oxides, chromium oxides and cobalt blue and also zinc sulfides, ultramarine, sulfides of the rare earths, bismuth vanadate and also carbon black, which is considered a pigment for the purposes of this invention.
  • Particular carbon blacks are the acidic to alkaline carbon blacks obtained by the gas or furnace process and also chemically surface-modified carbon blacks, for example sulfo- or carboxyl- containing carbon blacks.
  • Suitable organic pigments include, for example, those of the monoazo, disazo, laked azo, ⁇ -naphthol, Naphthol AS, benzimidazolone, diazo condensation, azo metal complex, isoindolinone and isoindoline series, also polycyclic pigments for example from the phthalocyanine, quinacridone, perylene, perinone, thioindigo, anthraquinone, dioxazine, quinophthalone and diketopyrrolopyrrole series.
  • Suitable pigments also include solid solutions of the pigments mentioned, mixtures of organic and/or inorganic pigments with organic and/or inorganic pigments such as, for example, carbon black coated metal, mica or talc pigments, for example mica CVD-coated with iron oxide, and also mixtures between the pigments mentioned.
  • Other suitable pigments include laked dyes such as Ca, Mg and Al lakes of sulfo- and/or carboxyl- containing dyes.
  • pigments from the group of the azo metal complex pigments or their tautomeric forms which are known.
  • Other suitable pigments include, for example, metal flake pigments of, for example, aluminum, zinc, or magnesium. It is also possible that the metal flake, particularly aluminum flake, could be leafing or non-leafing.
  • Suitable additives which may be present in accordance with the invention include surface-active additives such as emulsifiers and foam stabilizers.
  • surface-active additives such as emulsifiers and foam stabilizers.
  • examples include N-stearyl-N'.N'-bis-hydroxyethyl urea, oleyl polyoxyethylene amide, stearyl diethanol amide, isostearyl diethanolamide, polyoxyethylene glycol monoleate, a pentaerythritol/adipic acid/oleic acid ester, a hydroxy ethyl imidazole derivative of oleic acid, N- stearyl propylene diamine and the sodium salts of castor oil sulfonates or of fatty acids.
  • Alkali metal or ammonium salts of sulfonic acid such as dodecyl benzene sulfonic acid or dinaphthyl methane sulfonic acid and also fatty acids may also be used as surface-active additives.
  • Suitable foam stabilizers include water-soluble polyether siloxanes.
  • the structure of these compounds is generally such that a copolymer of ethylene oxide and propylene oxide is attached to a polydimethyl siloxane radical.
  • foam stabilizers are described, for example, in U.S. Patent 2,764,565.
  • other additives which may be used in the molding compositions of the present invention include known blowing agents including nitrogen, cell regulators, flame retarding agents, plasticizers, adhesion promoters, fillers and reinforcing agents such as glass in the form of fibers or flakes or carbon fibers.
  • the molded products of the present invention are prepared by reacting the components in a closed mold via the RIM process.
  • the compositions according to the present invention may be molded using conventional processing techniques at isocyanate indexes ranging from about 90 to 120 (preferably from 100 to 110.
  • Isocyanate Index also commonly referred to as NCO index
  • two separate streams are intimately mixed and subsequently injected into a suitable mold, although it is possible to use more than two streams.
  • the first stream contains the polyisocyanate component, while the second stream contains the isocyanate reactive components and any other additive which is to be included.
  • Isocvanate A an allophanate based on IPDI and isobutanol was prepared with by reacting 3148 g (28.3 eq.) IPDI with
  • the prepolymer of the allophanate was prepared by adding 196 g (2.0 eq.) trimethylol propane to the above allophanate.
  • the resultant prepolymer had an NCO content of
  • Polvol A a polyether polyol having a nominal functionality of about 3, an OH number of about 28, a molecular weight of about 6000, and comprising the reaction product of glycerin with propylene oxide and capped with ethylene oxide in the presence of a KOH catalyst
  • EG ethylene glycol
  • Catalyst A dimethyltin dilaurate catalyst, commercially available as Fomrez UL-28 from GE Silicones
  • Catalyst B 1 ,8-diazobicyclco(5.4.0)undec-7-ene catalyst, commercially available as Polycat DBU from Air
  • UV Stabilizer a combination ultraviolet stabilizer, commercially available as Tinuvin B 75 from Ciba Corp.
  • the polyurethane-forming systems of Examples 1-2 were injected using a MiniRIM cylinder machine.
  • the isocyanate-reactive materials and various additives were put into the B-side of the machine, and the appropriate quantities of the isocyanate component were loaded into the A-side.
  • the MiniRIM was equipped with a Hennecke mq8 Mixhead.
  • the B-side was preheated to 90 0 F and the A-side was heated to 90 0 F.
  • the materials were injected at an injection pressure of 200 bar and an injection rate of 400 grams/sec.
  • the material was injected into a flat plaque mold of 3 x 200 x 300 mm heated to about 165°F. After a 60 second dwell time, the part was demolded. Physical properties were determined in accordance with ASTM standards.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)
EP07763413A 2006-02-08 2007-02-05 Polyurethan-elastomere mit allophanat-modifizierten isocyanaten Withdrawn EP1984418A2 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US11/350,316 US20070185302A1 (en) 2006-02-08 2006-02-08 Polyurethane elastomers comprising allophanate modified isocyanates
PCT/US2007/003175 WO2007092459A2 (en) 2006-02-08 2007-02-05 Polyurethane elastomers comprising allophanate modified isocyanates

Publications (1)

Publication Number Publication Date
EP1984418A2 true EP1984418A2 (de) 2008-10-29

Family

ID=38236449

Family Applications (1)

Application Number Title Priority Date Filing Date
EP07763413A Withdrawn EP1984418A2 (de) 2006-02-08 2007-02-05 Polyurethan-elastomere mit allophanat-modifizierten isocyanaten

Country Status (9)

Country Link
US (1) US20070185302A1 (de)
EP (1) EP1984418A2 (de)
JP (1) JP2009526122A (de)
KR (1) KR20080100428A (de)
CN (1) CN101410431A (de)
BR (1) BRPI0707555A2 (de)
CA (1) CA2641427A1 (de)
RU (1) RU2008131912A (de)
WO (1) WO2007092459A2 (de)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070142610A1 (en) * 2005-12-15 2007-06-21 Harasin Stephen J Polyurethane elastomers comprising allophanate modified isocyanates
US8468968B2 (en) 2009-10-22 2013-06-25 Quest Inspar LLC Method and apparatus for lining pipes with isocyanate and hydroxyl-amine resin based on castrol or soy oil
CN111303373B (zh) * 2020-02-25 2022-07-12 万华化学集团股份有限公司 一种低色度脲基甲酸酯组合物及其制备方法和应用
CN114369189B (zh) * 2021-12-27 2023-12-19 万华化学集团股份有限公司 一种脱卤剂、制备甲苯二异氰酸酯和甲苯二异氰酸酯三聚体的方法

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4218543A (en) * 1976-05-21 1980-08-19 Bayer Aktiengesellschaft Rim process for the production of elastic moldings
US4269945A (en) * 1980-01-24 1981-05-26 The Dow Chemical Company Reaction injection molded polyurethanes employing aliphatic amine chain extenders
US4642320A (en) * 1983-11-02 1987-02-10 The Dow Chemical Company Reaction injection molded polyureas employing high molecular weight amine-terminated polyethers
DE3866247D1 (de) * 1987-01-14 1992-01-02 Bayer Ag Verfahren zur herstellung von polyurethan-formteilen.
US4764543A (en) * 1987-08-03 1988-08-16 The Dow Chemical Company Microcellular foamed or reaction injection molded polyurethane/polyureas employing amine terminated polymers and diamine chain extenders
GB9125918D0 (en) * 1991-12-05 1992-02-05 Ici Plc Reaction system for preparing polyurethane/polyurea
US5502147A (en) * 1993-12-21 1996-03-26 Bayer Corporation Aliphatic rim elastomers
US5502150A (en) * 1994-06-29 1996-03-26 Bayer Corporation Linear HDI urethane prepolymers for rim application
CA2174305C (en) * 1995-06-07 2007-07-03 Ronald A. Cageao Method of producing gaskets from polyurethane/urea compositions and gaskets produced therefrom
IN1997CH00157A (de) * 1996-10-01 2006-06-09 Recticel
US20070142610A1 (en) * 2005-12-15 2007-06-21 Harasin Stephen J Polyurethane elastomers comprising allophanate modified isocyanates

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2007092459A2 *

Also Published As

Publication number Publication date
KR20080100428A (ko) 2008-11-18
RU2008131912A (ru) 2010-03-20
BRPI0707555A2 (pt) 2011-05-10
CA2641427A1 (en) 2007-08-16
US20070185302A1 (en) 2007-08-09
WO2007092459A3 (en) 2008-08-28
WO2007092459A2 (en) 2007-08-16
JP2009526122A (ja) 2009-07-16
CN101410431A (zh) 2009-04-15

Similar Documents

Publication Publication Date Title
US5502150A (en) Linear HDI urethane prepolymers for rim application
EP1963390B1 (de) Rim-elastomere auf basis von isocyanureaten von isophorondiisocyanat und prepolymere davon
CN101321798B (zh) 耐候性提高的聚氨酯弹性体
EP1984418A2 (de) Polyurethan-elastomere mit allophanat-modifizierten isocyanaten
CN101321792B (zh) 包含脲基甲酸酯改性的异氰酸酯的聚氨酯弹性体
EP1963389B1 (de) Schnellhärtende aliphatische rim-elastomere
MX2008007217A (en) Fast curing aliphatic rim elastomers

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL BA HR MK RS

17P Request for examination filed

Effective date: 20090302

RBV Designated contracting states (corrected)

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

17Q First examination report despatched

Effective date: 20090820

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20091231